Hydroxydihydronorpolycyclopentadienes and method for their preparation



Patented Oct. 2, 1945 HYDROXYDIHYDRONORPOLYCYCIDPEN TADIENES AND METHOD FOR THEIR PREPARATION Herman A. Bruson, Philadelphia, la., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application February 20, 1943,

Serial No. 476,645

8 Claims. (Cl. 260-817) This invention relates to hydroxydihydronorpolycyclopentadien-es and a method for their preparation. I

In accordance with the disclosure of the present application, which is a continuation-in-part of copending application Serial No. 442,188, filed May 8, 1942, polymers of cyclopentadiene containing not mor than two double bonds per molecule are reacted with water in the presence of sulfuric acid to form unsaturated hydration products with a simultaneous molecular rearrangement of the original polycyclopentadiene ring system to a norpolycyclopentadiene ring system, as hereinafter described.

Typical polycyclopentadienes which can be used for the purpose of this invention are, for example, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, and homologues thereof, and include isomeric polycyclopentadiene and mixtures thereof. All of these possess two double bonds per molecule. Such polymers are crystalline solids obtainable by heating cyclopentadiene at 150-200 C. in a closed vessel. They have the general formula:

04x ag GB HOE (HaSOl) reacts only at the double bond of the endomethylene cycl with simultaneous rearrangement of the latter:

CH CH CHI CH HOE u H: Hi (H1 4) H H I H H 'lricyclopentadiene 01 CH CH CH c{l c l C! on H: H: l u n- -c on on \4 Hi Hydroxydihydronortricyclopontadiene or on on Hydroxydihydronortricydopentadiene Similarly tetracyclopentadiene and pentacyclopentadiene add water to form rearranged alcohols.

All of these alcohols are new substances. They are secondary alcohols of definite physical properties and chemical composition. In. view of the fact that they are derived from polycyclopentadienes but possess a new and diflerent ring system, they are referred to herein for the sake of brevity as "norpolycyclopentadiene" derivatives.

It is surprising that only one double bond adds the elements of water to the complete exclusion of the second double bond present in the molecule, even when an excess of hydrating agent is present, particularly since both double bonds are of the secondary type and are apparently equivalent.

In the preparation of the hydroxydihydronorpolycyclopentadienes ,of this invention, there may be used aqueous sulfuric acid of ,a wide range of concentration. In fact, it is possible to use 95%-100% sulfuric acid if care is taken tokeep the temperature low, as, for example, -20 C., and to hydrolyze subsequently the unstable intermediate sulfuric acid addition product by the addition of water. For practical purposes, however, it is advantageous to employ aqueous sulfuric acid of from about to about 50% H2804 content at temperatures between about 65 and 115 C., although both lower and higher temperatures are operative, the optimumyields being obtained'with aqueous %'35% sulfuric acid at 901l0 C. It has been found desirable to use a full molecular proportion of H2804 per mol of polycyclopentadiene. This appears to lessen or prevent the formation of ethers of hydroxydihydronorpolycyclopentadienes which are otherwise formed simultaneously with the alcohols desired. It is to be understood, however, that the choice of temperature, proportions, and

concentrations is only incidental to the spirit of the invention, which is not to beconsidered as limited by these features, since good yields are possible with wide variations in working conditions.

In order to promote good contact between the organic solvents may be used, such as, by way perature used, and are thus rendered amenable to the hydration. When the reaction mixture is washed and vacuum-distilled, the individual hydroxydihydronorpolycyclopentadienes can be separated from one another.

The following examples illustrate this invention. Parts are by weight.

Example 1 A mixture of 264 parts of dicvclopentadienc and 800 parts of aqueous 25% sulfuric acid was stirred rapidly and heated under areflux condenser at 104-10'l C.'for four and one-half hours. The aqueous sulfuric acid layer was then separated and the oil layer was washed successlvely with hot water, dilute soda solution, and

finally again with hot water. The oil was driedand distilled in vacuum at 0 mm. absolute pressure of mercury. The productwhich over between 105 and 115 C./8 mm. was hydroxydihydronordicyclopentadiene.

88.4% of theory. 1 Example 2 i A mixture of 264 parts of dicyclopentadiene and 81'! parts of aqueous 30% acid was stirred and heated for five hours at 94-98 C. on a steam bath in a vessel attached to a reflux condenser. The reaction product was washed and worked up as in Example 1. The yield of hydroxydihydronordicyclopentadiene was 249 parts. or 83% of theory.

Example 3 A mixture of 264 parts of dicyclopentadiene and 1,000 parts of aqueous 20% sulfuric acid was stirred for four and one-quarter hours at 95 C. and was worked up as in Example 1. The

yield of hydroxydihydronordicyclopentadiene boiling between and -a mm. was

parts.

Example 4 Example 5 A mixture of 132 parts of dicyclopentadiene and 250 parts of aqueous 50% sulfuric acid was stirred rapidly at 95 C. for two and one-half hours. An equal volume of water was then added and steam passed through the mixture whilethe volatile steam distillate was condensed. The oil layer of the distillate was separated and redistilled in vacuum to yield about 35 parts of hydroxydihydrodicyclopentadiene.

7 Example 6 To a solution of 132 parts of dicyclopentadiene in 250 parts of methylcyclohexane' cooled to 5 C., 106 parts of 95% sulfuric acid 1 was added gradually while the reaction mixture was stirred and maintained at 5-10 C. The mixture was stirred for twenty minutes, then was poured into ice water and steam-distilled. Considerable dark resin separated during the steaming. The mixture of hydroxydihydronordicyclopentadiene and methylcyclohexane which distilled over with the steam was condensed and separated by distillation into pure. hydroxydihydronordicyclopentadiene which boiled at 95-l00 C./1 mm. and gave an iodine number of 164 by the Hanus method (theory It was fa viscid, colorless oil. The yield was 250 partaf'ot ii water.

' assures trample 7 (a) a mixture of 114 parts of a-tricyclopentadiene and 150 parts of 40% sulfuric acid was rapidly stirred and heated under reflux for five hours at 115-l25 C. The dark viscous mass was stirred with hot water and the oil layer separated with the aid of -toluene. The toluene solution was washed, first with hot water, then with dilute soda solution, and finally with hot The toluene was evaporated oil and the residual, dark, very viscous mass distilled under reduced pressure at 2 mm. absolute pressure of mercury. V

Hydroxydihydronortricyclopentadiene distilled over as a colorless viscous oil at l60'-170'/2 mm. in a yield amounting to 41 parts. Upon redistiilation at 11 mm., it boiled at 180-186 C. 1 It crystallizes on standing to a wax-like solid which can be recrystallized from nitroethane in the form of colorless needles, melting point 115 C. It is very soluble in methanol, benzene, ether, or acetone.

A higher boiling fraction, boiling point 260- 280/2 mm., was also obtained as a viscous pale yellow liquid which rapidly solidified to a hard, transparent, resinous solid in a yield of 32 parts. It consists essentially of the ether of the above alcohol, having the formula (b) In the same manner, a mixture of 99 parts of tricyclopentadiene (mostly p-isomer) and 167 parts of aqueous 30% sulfuric acid was boiled for seven hours at 109-115 C. under reflux with rapid stirring. The viscous mass was cooled, dissolved in toluene and washed several times with hot water followed by a wash with soda solution and finally water. Upon evaporation of the toluene, 100 parts of a black tar-like mass was obtained which, upon distillation under reduced pressure at 2 mm., yielded 42 parts of hydrox'ydihydronortricyclopentadiene, which, upon recrystallization from nitroethane, formed colorless needles, melting point 98 C.

Example 8 (75 parts) came over at 90-100' C. at 3 The fraction boiling at 220"-240 C./8 mm. was a pale yellow, transparent solid, having a hydroxyl number of 190 (theory for hydroxy-dihydronortetracyclopentadiene is 199). It is readily soluble in alcohol and can be recrystallized from l-nitropropane. Y

(b) In the same manner, hydroxydihydronorpentacyclopentadiene is obtained as a hard, transparent solid by heating parts 0! Pen acyclopentadiene with 100 parts of dicyclopentadime and 330 parts of 30% sulfuric acid, washing as above, and distilling oi! the hydroxydihydronordicyclopentadiene in vacuo. The hydroxydihydronorpentacyclopentadiene boils above 960 C. at 1 mm.

Pure hydroxydihydronordicyclopentadiene, as

obtained by careful vacuum distillation of any of the above preparations, is a colorless, rather visoid liquid boiling at low-104- C./'l mm. or 240' C4773 mm. It does not solidify or crystalline at 0' C. It has the formula CuHuO and the following constants: di"l.0'l'l3; a 1.5946. It is insoluble in water but miscible in all proportions with methanol, acetone, dioxane, benzene, ether, kerosene, petroleum oils, castor oil, and the like. It possesses a camphoraceous odor, susgestive of borneol. with phthalic anhydride, it gives a crystalline mono-acid phthalate which melts at 139-141 C. with phenyl isocyanate it yields a crystalline phenyl urethane having a melting point of 160-165 C. Upon oxidation with chromic acid in acetic acid at 50 C., it yields the corresponding ketodihydronordicyclopentadione as a colorles liquid, boiling at 109' C./13

mm., possessing values of d4 1.0759 and n 1.5146, and yielding a-semicarbazonewhich melts at 200 C. and an oxime which melts at 105- 106 C. Upon catalytic hydrogenation, hydroxydihydronordicyclopentadiene yields the corresponding hydroxytetrahydronordicyclopentadiene, which is a crystalline solid having a melting point of 53 C.

The hydroxydihydronorpolycyclopentadienes are useful as solvents, as plasticizers, as hydraulic fluids, and as components of hydraulic fluids in brake or recoil mechanisms, as components for preparing synthetic waxes and resins, and as intermediates for drugs, wetting agents, insecticides, emulsifying agents, detergents, bactericides, and cosmetics. As a solvent, hydroxydihydronordicyclopentadiene is particularly useful in printing inks because of its high boiling point and dissolving power for resins and oils. Chemically, the hydroxydihydronorpolycyclopentadienes react with organic monocarboxylic acids, such as acetic, crotonic, valeric, etc., or polycarboxylic acids, such as phthalic, succinic, maleic, oxalic, or tricarballylic, to form esters useful in the plastic arts.

The new alcohols of this invention areconveniently represented by the following general formula, which is in accord with the most probable structure of these compounds:

on on c ..(l\ l\ OH H. l H. l 110 n- I n a CH: OH

LI ll :Ha I

wherein Colitis a propenylene group which in coniimction with the adjoining carbon atoms forms a cyclopenteno group.

The double bond in the terminal live-membered cycle is reactive with such addends as hydrogen, chlorine, bromine, iodine, iodine bromide, iodine chloride, thiocyanogen. etc.

Although in the above examples practically pure polycyclopentadienes have been used, the process shown may also be applied to mixtures of hydrocarbons which contain 5% or more of the polycyclopentadienes having two double bonds per molecule, such as are obtained in the thermal cracking of petroleum or in the manufacture of water gas. The reaction of the polycycloq pentadienes provides a new means for separating the components 01' mixtures of unsaturated hydrocarbons and gives new utility to such products.

I claim:

1. A method for preparing hydroxydihydro- -norpolycyclopentadienes having a terminal fivemembered cycle containing a double bond, which comprises heating aqueous sulfuric acid containing from about 20% to about 50% H2804 with a crystalline polymer of cyclopentadiene having the i'ormula:

formula:

4 ke 9/ l l in H assures whereinnis anumberirom 0to3,'inclusive,ata temperature between about 65' and 115' C.

3. A method for preparing hydroxydihydronordicyclopentadiene having a terminal iivemembered cycle containing a double bond, which comprises reacting dicyclopentadiene with aqueous sulfuric acid.

4. A method for preparing hydroaydihydronortricyclopentadiene having a terminal themembered cycle containing a double bond, which comprises reacting trlcyclopentadiene with aqueous sulfuric acid.

5. A method for preparing hydroxydihydronordicyclopentadiene having a terminal iivemembered cycle containing a double bond, which comprises heating dicyclopentadiene with approximately a molecularly equivalent quantity of aqueous sulfuric acid or about 20% to H3804 content at a temperature from about to 115 C.

6. An acid-catalysed, addition-rearrangement product of water and a crystalline polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule, said product being a hydrowdihydronorpoly yclopentadiene, a compound having a secondary alcoholic hydroxyl group in one terminal iive-membered cycle and a cyclopenteno ring as an opposite terminal cycle.

7. An acid-catalysed. addition-rearrangement product of water and dlcyclopentadiene, said product, when pure, being a colorless oil boiling at 102-104 C./'! mm., and being hydroxydihydrv, nordicyclopentadiene. a compound having a sec ondary alcoholic hydroxyl group in one terminal flve-membered cycle and a cyclopenteno ring as an opposite terminal cycle.

8. An acid-catalysed, addition-rearrangement product or water and tricyclopentadiene having two double bonds and one to tour endomethylcne cycles per molecule, said product, when pure, being a colorless crystalline solid melting at 115 C. and boiling at l-l85 C./ll and being hydroxydihydronortricyclopentadiene, a compound having a secondary alcoholic hydroxyl group in one terminal cycle and a cyclopenteno ring as an opposite terminal cycle.

HERMAN A. BRUS ON'. 

